CN104388998B - A kind of method that porous nano aluminum oxide is prepared in room temperature electro-deposition - Google Patents
A kind of method that porous nano aluminum oxide is prepared in room temperature electro-deposition Download PDFInfo
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- CN104388998B CN104388998B CN201410656170.5A CN201410656170A CN104388998B CN 104388998 B CN104388998 B CN 104388998B CN 201410656170 A CN201410656170 A CN 201410656170A CN 104388998 B CN104388998 B CN 104388998B
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Abstract
A kind of method that porous nano aluminum oxide is prepared in room temperature electro-deposition, the method relating to preparing nano aluminium oxide, including following preparation process: the preparation of plating solution, Copper substrate process, constant current electro-deposition, are the ratio of 2:1 ~ 4:1 according to mol ratio, weigh anhydrous Aluminum chloride and lithium aluminium hydride reduction respectively；By copper sheet, sand papering with 400,800 and 1200 mesh is smooth successively, then electrochemical deoiling is carried out, remove the greasy dirt on copper sheet surface, carry out pre-etching with dilute sulfuric acid again and weak corrosion removes oxide-film, then ultrasonic cleaning in distilled water and acetone, the most again with distilled water flushing, put into after washing in vacuum drying chamber and be dried, stand-by；Making anode with graphite, copper sheet makees negative electrode, and controlling current density is 1 10 milliamps per square centimeter, carries out electro-deposition, can obtain the pure and uniform aluminum oxide of pore size under air conditions.The method low cost, technology controlling and process is simple, and the aluminum oxide pore size of production is uniform.
Description
Technical field
The present invention relates to a kind of method preparing nano aluminium oxide, particularly relate to a kind of room temperature electro-deposition and prepare porous and receive
The method of rice aluminum oxide.
Background technology
Nano material receives much concern due to its important performance with at the extensively application potential in many fields.Porous oxidation
Aluminium is that a kind of research to obtain the most nano materials, by controlling preparation condition, can obtain the regular nanometer of different pore size
Cavernous structure, size from several, tens the most available to hundreds of nanometers.Al2O3Material has high intensity, high rigidity, anti-corruption
The characteristics such as erosion, high temperature resistant, non-oxidizability, Al2O3Powder be prepare catalyst and carrier thereof, dental material, special cermacis important
Raw material.Al2O3It is widely used to the aspects such as structural ceramics, catalyst carrier, fine ceramics, micro porous filtration.Additionally, integrated
The new materials such as circuit base material, fast-ionic conductor composite, fluorescent material, moisture-sensitive sensor and infrared absorbing material
Field also receives much concern.In the last few years, about the research of alumina adsorption heavy metal it has been reported that Woelm Alumina is as high property
Adsorbent aspect can show huge potentiality.It possesses the high surface that other water-purifying material can not be compared, and is removing weight
Metal ion, organic pollution and bacterium aspect show huge potential.Porous Al2O3Act not only as excellent catalysis
Agent and carrier thereof, be applied to Slow/Controlled Release Drug preparation, again because its loose structure, can save raw material, reduce and produce into
This.Up to the present, various technology have been used to prepare Woelm Alumina, including: template auxiliary law, sol-gal process,
Hydrothermal synthesis method, electrochemical deposition method etc..In all of method, electrochemical deposition method most attraction, this method can control
The crystallization process of nano structure membrane, and electrochemical deposition method be a kind of simple, quickly, low cost prepare large area film
Method, this method can be carried out in the case of chilling process, any substrate shapes.By controlling sedimentation potential, current density
Can be good at controlling the speed of growth and the film thickness of crystal grain with concentration of electrolyte.
Summary of the invention
It is an object of the invention to provide a kind of method that porous nano aluminum oxide is prepared in room temperature electro-deposition, the method utilizes
Room temperature electrolyte system (AlCl3-LiAlH4-THF-benzene), control the key factors such as current density, solution composition and sedimentation time
Prepare Woelm Alumina.The method low cost, technology controlling and process is simple, and the aluminum oxide pore size of production is uniform.
It is an object of the invention to be achieved through the following technical solutions:
A kind of method that porous nano aluminum oxide is prepared in room temperature electro-deposition, described method includes following preparation process:
A. the preparation of plating solution:
In the glove box of full argon gas, it is the ratio of 2:1 ~ 4:1 according to mol ratio, weighs anhydrous Aluminum chloride and hydrogen respectively
Change aluminium lithium；Lithium aluminium hydride reduction is joined in oxolane, prepare the tetrahydrofuran solution of lithium aluminium hydride reduction；Anhydrous Aluminum chloride is added
In benzene, and being slowly added dropwise oxolane in the case of stirring, along with the addition of oxolane, insoluble aluminium chloride is the most molten
Solve；Finally it is slowly added dropwise the tetrahydrofuran solution of lithium aluminium hydride reduction, stirring while adding；This process releases substantial amounts of heat, be at frozen water
Carry out under bath cooling condition, during liquid temp to be electrolysed to room temperature, be placed on mix and blend 3 hours on magnetic stirring apparatus, this mistake
The use ratio of journey benzene and oxolane is 4:1；
B. Copper substrate processes:
By copper sheet, sand papering with 400,800 and 1200 mesh is smooth successively, then carries out electrochemical deoiling, removes copper sheet table
The greasy dirt in face, then carry out pre-etching and weak corrosion removing oxide-film, then ultrasonic cleaning in distilled water and acetone with dilute sulfuric acid,
The most again with distilled water flushing, put into after washing in vacuum drying chamber and be dried, stand-by；
C. constant current electro-deposition:
Making anode with graphite, copper sheet makees negative electrode, controls current density and is 1-10 milliamps per square centimeter, under air conditions
Carry out electro-deposition, the pure and uniform aluminum oxide of pore size can be obtained.
Advantages of the present invention with effect is:
The method utilizes room temperature electrolyte system (AlCl3-LiAlH4-THF-benzene), control current density, solution composition and
The key factors such as sedimentation time prepare Woelm Alumina.Owing to the oxidation-reduction potential of Al is born very much, and this element
Very active, if the electrodeposition process of Al has trace water, Copper substrate produces substantial amounts of bubble hydrogen, by room temperature condition
The bubble hydrogen generated in lower electrochemical deposition process can prepare Woelm Alumina as dynamic template.Gas during deposition
Bubble is by the Interface Moving towards electrolyte Yu gas, so place does not has the metal ion that can reduce, therefore towards bubble direction
Metal can not grow, thus causes metal can only precipitate and be formed the Woelm Alumina of nano-scale between bubble.Kong Jie
Structure is the competition between electrodeposit reaction and evolving hydrogen reaction and produces.The method low cost, technology controlling and process is simple, the oxygen of production
Change aluminium pore size uniform.
Accompanying drawing explanation
Fig. 1 is the SEM photograph schematic diagram of 20000 times of samples of multiplication factor of the present invention；
Fig. 2 is the SEM photograph figure of 50000 times of lower samples of multiplication factor of the present invention；
Fig. 3 is the EDS energy spectrum analysis figure of A point in Fig. 2 of the present invention.
Detailed description of the invention
Illustrated embodiment below in conjunction with the accompanying drawings, the invention will be further described.
The formation mechanism of electrodeposit reaction mechanism and aluminum oxide is as follows:
(1) when lithium aluminium hydride reduction is dissolved in liquor alumini chloridi, there is following reaction,
LiAlH4+4AlCl3=4AlHCl2+LiAlCl4
Cathode reaction mechanism is represented by,
AlHCl2+3e-=H-+2Cl-+Al ↓
(2) newly-generated aluminium occurs to react generation aluminum oxide as follows under certain condition,
2Al(s) +3H2O(l) )= Al2O3(s) + 3H2(g) (1)
4Al(s) + 3O2(g) = 2Al2O3 (s) (2)
Enforcement step:
A kind of method that porous nano aluminum oxide is prepared in room temperature electro-deposition is as follows:
(1) preparation of plating solution
In the glove box of full argon gas, it is the ratio of 2:1 ~ 4:1 according to mol ratio, weighs anhydrous Aluminum chloride and hydrogen respectively
Change aluminium lithium.Lithium aluminium hydride reduction is joined in oxolane, prepare the tetrahydrofuran solution of lithium aluminium hydride reduction.Anhydrous Aluminum chloride is added
In benzene, and being slowly added dropwise oxolane in the case of stirring, along with the addition of oxolane, insoluble aluminium chloride is the most molten
Solve.Finally it is slowly added dropwise the tetrahydrofuran solution of lithium aluminium hydride reduction, stirring while adding.This process releases substantial amounts of heat, be at frozen water
Carry out under bath cooling condition, during liquid temp to be electrolysed to room temperature, be placed on mix and blend 3 hours on magnetic stirring apparatus, this mistake
The use ratio of journey benzene and oxolane is 4:1.
(2) Copper substrate processes
By copper sheet, sand papering with 400,800 and 1200 mesh is smooth successively, then carries out electrochemical deoiling, removes copper sheet table
The greasy dirt in face, then carry out pre-etching and weak corrosion removing oxide-film, then ultrasonic cleaning in distilled water and acetone with dilute sulfuric acid,
The most again with distilled water flushing, put into after washing in vacuum drying chamber and be dried, stand-by.
(3) constant current electro-deposition
Making anode with graphite, copper sheet makees negative electrode, controls current density and is 1-10 milliamps per square centimeter, under air conditions
Carry out electro-deposition (this electrolyte system water imbibition is strong, and the water in air is absorbed and can participate in reacting), can obtain pure and
The uniform aluminum oxide of pore size.
The present invention is according to the electrochemical characteristic of Al, i.e. the oxidation-reduction potential of Al is born very much, and this element is very
Vivaciously, under air conditions, electro-deposition is owing to there being water will produce substantial amounts of bubble hydrogen on matrix, by electrochemical deposition mistake
The bubble hydrogen generated in journey prepares Woelm Alumina as dynamic template.During deposition, bubble will be towards electrolyte and gas
The Interface Moving of body, owing to not having the metal ion that can deposit herein, therefore can not grow towards bubble direction metal, thus
Cause metal can only precipitate and be formed the Woelm Alumina of nano-scale between bubble.Pore structure is electrodeposit reaction and analysis
Hydrogen reaction between competition and produce.The method low cost, technology controlling and process are simple, and the aluminum oxide of production is pure and pore size
Uniformly.
Embodiment 1:
(1) preparation of plating solution:
In the glove box of full argon gas, weigh 8 grams of anhydrous Aluminum chlorides and 0.57 gram of lithium aluminium hydride reduction respectively.By lithium aluminium hydride reduction
Join in the oxolane of 8 milliliters, prepare the tetrahydrofuran solution of lithium aluminium hydride reduction.Anhydrous Aluminum chloride is joined 40 milliliters of benzene
In, and it is slowly added dropwise 2 milliliters of oxolanes in the case of stirring, along with the addition of oxolane, insoluble aluminium chloride is gradually
Dissolve.Finally it is slowly added dropwise the tetrahydrofuran solution of lithium aluminium hydride reduction, stirring while adding.This process releases substantial amounts of heat, be at ice
Carry out under water-bath cooling condition, during liquid temp to be electrolysed to room temperature, be placed on mix and blend 3 hours on magnetic stirring apparatus.
(2) Copper substrate processes:
By copper sheet, sand papering with 400,800 and 1200 mesh is smooth, to improve the flatness on plating piece surface successively.Then
Carry out electrochemical deoiling, remove the greasy dirt on plating piece surface, it is ensured that coating and the degree of adhesion of matrix.Pre-etching is carried out again with dilute sulfuric acid
And weak corrosion removes oxide-film, then ultrasonic cleaning in water and acetone, rinse in distilled water the most again, put into true after washing
Empty drying box is dried, stand-by.
(3) constant current electro-deposition:
Making anode with graphite, copper sheet makees negative electrode, controls current density 2 milliamps per square centimeter, carries out electricity under air conditions
Deposition, can obtain the pure and uniform aluminum oxide of pore size.
Embodiment 2:
(1) preparation of plating solution:
In the glove box of full argon gas, weigh 8 grams of anhydrous Aluminum chlorides and 0.57 gram of lithium aluminium hydride reduction respectively.By lithium aluminium hydride reduction
Join in the oxolane of 8 milliliters, prepare the tetrahydrofuran solution of lithium aluminium hydride reduction.Anhydrous Aluminum chloride is joined 40 milliliters of benzene
In, and it is slowly added dropwise 2 milliliters of oxolanes in the case of stirring, along with the addition of oxolane, insoluble aluminium chloride is gradually
Dissolve.Finally it is slowly added dropwise the tetrahydrofuran solution of lithium aluminium hydride reduction, stirring while adding.This process releases substantial amounts of heat, be at ice
Carry out under water-bath cooling condition, during liquid temp to be electrolysed to room temperature, be placed on mix and blend 3 hours on magnetic stirring apparatus.
(2) Copper substrate processes:
By copper sheet, sand papering with 400,800 and 1200 mesh is smooth, to improve the flatness on plating piece surface successively.Then
Carry out electrochemical deoiling, remove the greasy dirt on plating piece surface, it is ensured that coating and the degree of adhesion of matrix.Pre-etching is carried out again with dilute sulfuric acid
And weak corrosion removes oxide-film, then ultrasonic cleaning in water and acetone, rinse in distilled water the most again, put into true after washing
Empty drying box is dried, stand-by.
(3) constant current electro-deposition:
Making anode with graphite, copper sheet makees negative electrode, controls current density 6 milliamps per square centimeter, carries out electricity under air conditions
Deposition, can obtain the pure and uniform aluminum oxide of pore size.Sample SEM photograph and EDS collection of illustrative plates are shown in accompanying drawing 1, Fig. 2 and Fig. 3.
Table 1 is sample EDS EDAX results.
Fig. 1 and Fig. 2 is respectively the SEM photograph of 20000 times and 50000 times lower samples of multiplication factor, as can be seen from Figure 1
This product is porous material.As can be seen from Figure 2 this material is made up of the thin slice of about 25 nanometer thickness.Fig. 3 is A point in Fig. 2
EDS energy spectrum analysis figure.The element that mainly comprises of this material is aluminium and oxygen as can be seen from Figure 3.Sample EDS EDAX results is shown in
Table 1, is mainly composed of aluminum oxide according to what the data analysis of table 1 and reaction mechanism understood this material.
The EDS EDAX results of table 1 A point
| Element | Weight | Atom |
| Percentage | Percentage | |
| C K | 1.81 | 2.99 |
| O K | 49.51 | 61.32 |
| Al K | 48.39 | 35.53 |
| Cl K | 0.28 | 0.16 |
| Total amount | 100.00 |
Claims (1)
1. the method that porous nano aluminum oxide is prepared in a room temperature electro-deposition, it is characterised in that described method includes following preparation
Process:
A. the preparation of plating solution:
In the glove box of full argon gas, it is the ratio of 2:1 ~ 4:1 according to mol ratio, weighs anhydrous Aluminum chloride and aluminum hydride respectively
Lithium；Lithium aluminium hydride reduction is joined in oxolane, prepare the tetrahydrofuran solution of lithium aluminium hydride reduction；Anhydrous Aluminum chloride is joined benzene
In, and it is slowly added dropwise oxolane in the case of stirring, along with the addition of oxolane, insoluble aluminium chloride gradually dissolves；
Finally it is slowly added dropwise the tetrahydrofuran solution of lithium aluminium hydride reduction, stirring while adding；This process releases substantial amounts of heat, cold at ice-water bath
But carry out under the conditions of, during liquid temp to be electrolysed to room temperature, be placed on mix and blend 3 hours on magnetic stirring apparatus, this process benzene
It is 4:1 with the use ratio of oxolane；
B. Copper substrate processes:
By copper sheet, sand papering with 400,800 and 1200 mesh is smooth successively, then carries out electrochemical deoiling, removes copper sheet surface
Greasy dirt, then carry out pre-etching and weak corrosion removing oxide-film, then ultrasonic cleaning in distilled water and acetone with dilute sulfuric acid, then
Again with distilled water flushing, put into after washing in vacuum drying chamber and be dried, stand-by；
C. constant current electro-deposition:
Making anode with graphite, copper sheet makees negative electrode, controls current density and is 1-10 milliamps per square centimeter, carries out under air conditions
Electro-deposition, can obtain the pure and uniform aluminum oxide of pore size.
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2014
- 2014-11-18 CN CN201410656170.5A patent/CN104388998B/en not_active Expired - Fee Related
Patent Citations (6)
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| US4066515A (en) * | 1975-08-21 | 1978-01-03 | Siemens Aktiengesellschaft | Apparatus and method for the electrodepositing of aluminum |
| US4176034A (en) * | 1977-04-15 | 1979-11-27 | Siemens Aktiengesellschaft | Apparatus for the electrodeposition of aluminum |
| SU1401075A1 (en) * | 1986-11-27 | 1988-06-07 | Институт Физической Химии Ан Ссср | Method of producing ester-hydride aluminium-poating electrolyte |
| SU1539239A1 (en) * | 1988-05-07 | 1990-01-30 | Институт Физической Химии Ан Ссср | Method of alminium-plating in organic electrolytes |
| US6652730B1 (en) * | 1998-12-01 | 2003-11-25 | Studiengesellschaft Kohle Mbh | Aluminum organic electrolytes and method for electrolytic coating with aluminum or aluminum-magnesium-alloys |
| CN103334132A (en) * | 2013-07-17 | 2013-10-02 | 沈阳大学 | Method for preparing aluminum-magnesium alloy membrane through electro-deposition at room temperature |
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| 铝及铝镁合金的室温电沉积制备;阚洪敏;《沈阳大学学报（自然科学版）》;20131231;第25卷(第6期);第441-445 * |
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